Green anthracene dye and process of making same.



U ITED STATES PATENT Fries.

SODA'FABRIK, OF LUDWIGSI-IAFEN-ON-THE-RHINE, GERMANY, A CORPO- RATION.

GREEN ANTHRACENE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent N 0. 723,125, dated March 17, 1903.

l Application filed November 1, 1901. Serial No. 80,835. ($pecimens.)

To all whom it may concern:

Be it known that I, OSCAR BALLY, doctor ofphilosophy and chemist, a citizen of the Swiss Republic, residing at Mannheim, in the Grand Duchy of Baden, Germany, have invented new and useful Improvements in Coloring-Matters of the Anthracene Series and Processes of Producing the Same, of which the following is a specification.

IO According to a previous invention of mine sulfonated coloring-matters of the anthracene series can be obtained by condensing the sulfo-acids of aromatic amido bodies with nitroanthraquinone derivatives. I have now found 1'5 that these condensation products can easily be transformed into halogen derivatives soluble in water which are of themselves coloring-matters and are also capable of condensingwith aromatic amins to form new colorzo ing-matters of various shades. These new halogen bodies can be prepared by treating the aforementioned sulfonated coloring-matters in the condition eitherof the free acid or of their salts with chlorin or bromin in aqueous solution or suspension or in the dry condition. The condensation of the halogen bodies thus formed with amido bodies can be effected by melting them with the amin chosen, or the solutioufor instance, in waten-ofthehalogenizedsulfmacidcanbeboiled with the amidobody for a sufficient length of time or preferably heated under pressure in aclosed vessel,whereby the addition of such bodies as sodium acetate or calcium acetate, sodium carbonate, and the like frequently afieots the reaction in a favorable manner. The new coloring-matters thus obtaihed can be employed for dyeing mordanted and unmordant-ed wool. They are as a rule sufliciently soluble in water for dyeing purposes; but if not they can be further sulfonated in the known manner.

The following examples will serve to further illustrate the nature of my invention and 5 the manner in which the same may be carried into practical effect; but the invention is not confined to these examples. .The parts are the coloring-matter which can be obtained from 1.S-dinitro-anthraquinone and sodium sulfanilate in thirty (30) parts of water at ordinary temperature and gradually add three (3) parts of bromin While stirring. Con tinue to stir for twenty-four (24.) hours. The bromid thus formed can be precipitated from the solution by means of common salt.

Example 2. Bromination of the condensa- 6o tionproduct-ofmono-nitro-.anthraquin0nesulfo-acid and sodium sulfanilate-Dissolve ten (10) parts of the coloring-matter obtainable from crude mono-nitro-anthraquinone sulfoacid and sodium sulfanilate in two hundred (200) parts of water and treat it at'ordin'ary" temperature with eight (8) parts of bromin. When the reaction is ended, salt out the reaction product by means of common salt. The condensation products of beta-nitro-an- 7o thraquinone sulfo-acid and sulfanilic acid or of nitro-anthraquinone sulfa-acid and metanilic acid can be treated with bromin in a similar manner.

Example 3. Chlorination of the eondensation product of mono-nitro-anthraquinone sulfa-acid and sodium sulfanilate.Dissolve one hundred (100) parts of the coloring-matter used as initial material in the foregoing Example 2 in two thousand (2,000) parts of hydrochloric acid, (containing about thirtytwo per cent. of H01.) To this solution add gradually twenty-four (24) parts of potassium chlorate, taking care that the temperature does not rise above thirty (30) degrees centi- 7 grade. In a short time the color of the solution changes from violet-red to yellow-red. Salt out the chlorination product formed.

Instead of employing the isolated initial material the crude coloring-matter melt can go be directly treated with halogens, as set forth in the following example:

Example 4. Production of the coloring-matter from, nitro-anthraquinone, sulfo-acid and sodium sulfanilate and chlorination of the 5 same in one operation-Heat one hundred parts of crude nitro-anthraquinone sulfo-acid, sixty-five (65) parts of sodium sulfanilate, (containing water of crystallization,)

and five hundred (500) parts of water in an 100 autoclave until no more coloring-matter is formed. Dissolve the reaction mass when cold in sixteen hundred (1,600) parts of hydrochloric acid (containing about thirty-two per cent. of H01) and gradually add a solution of twenty-four (24:) parts of potassium chlorate in four hundred (400) parts of water while keeping the temperature below thirty (30) degrees centig'rade. Salt out the ch rinated product formed after twenty-four (24) hours stirring.

The following table gives some of the properties of some of the halogenized bodies which can be obtained in the manner set forth:

Solution in Halo en derivative. Sulfuric acid, Sulfuric acid b Water. Alcohol. (ninety-six per (ninety-six per cent.) s fg cent.) and boric acid.

1. Brom derivative obtainable according to Red-brown Brown-red Olive brownnn Brown-violet Fairlysoluble; red

Example 1. brown. 2. Brom derivative obtainable according to Yellgwish Yellow-red Brown Bluish cherry-red... Hardly soluble.

Examp e 2. re 3. Brom derivative obtainable according to Yellowu-ed. Yellow-red Reddish brown. Bluish cherry-red... Slightly soluble; Example 2 from the condensation prodred-orange. not of beta-nitro-anthraquinone sulfoacid and sulfanilic acid. 4. Brom derivative obtainable according to Cherry-red. Red-orange Bro\vn-olive Bluish cl1erry-red Almost insoluble.

Example 2 from the condensation product of crudenitro-anthraquinone sulfoacid and metanilic acid. 5. Ohlor derivative of Example 3 Yellow-red. Brown Brown Fuchsin-red Slightly soluble;

brown-yellow. 6. Ohlor derivative of Example 4 Fuchsin-red Red-yellow. Brown Fuchsin-red Hardly soluble.

Escamplc 5. Condensation of brom-s-ulfam'lido-anthraquinone snlfo-acz'd with paratolu'idin.Heat fifty (50) parts of brom-sulfanilido-anthraquinone-mono-sulfo-acid, (obtainable as described in Example 2,) twenty-five parts of paratoluidin, one hundred (100) parts of calcium-acetate solution, (twenty per cent.,) and six hundred and fifty (650) parts of water in an enameled autoclave at a temperature of one hundred and eighty to two hundred degrees centigrade (180 to 200 cen tigrade) until no increase in the amount of the coloring-matter formed takes place. Extract the reaction mass with hot alcohol. A difficultly-soluble coloring-matter remains undissolved, which I will call product A3. A product goes into solution, which I will call product B. It separates from the cold alcoholic solution in crystalline form.

Example 6. Condensation of chlor-snlfant'lquinone sulfo-acid obtainable as described in Example 4, one (1) part of anilin, and five (5) parts of water in an autoclave at a temperature of about one hundred and eighty (180) degrees cen tigrade and proceed further as in Example 5. In this case also two coloring-matters are formed, one almost insoluble, the other soluble in alcohol. I will term them product 0 and product D, respectively.

Example '7. Sulfonat'ion of product A of Example 5.Introduce one (1) part of the coloring-matter product A obtainable as described in Example 5 into twenty (20) parts of monohydrate sulfuric acid and heat at a temperature of thirty-five to forty degrees centigrade until a test sample is easily soluble in water. Dilute the melt with icewater and salt out the sulfo-acid formed.

The following table indicates some of the tdo-anthraqmnone sulfo-actd wnfh anzltn. properties of some of the coloring-matters ob- Heat one (1) part of chlor-sulfanllido-anthratainable according to my invention:

Behavior towards mt y Condensation product Appearg ig chromeance. Water Sodium Caustic Alcohol Glacial ace- Nitrocgulfuric mordantcarbonate. soda. tic acid. benzene. 0 ed wool.

acid, (96 A.)

1. Paratoluidin brom- As p ow- Difficultly Insoluble Difficultly soluble On boiling Violet B 1 i g h t sulfanil1d0-an thrader viosoluble. blue. f a i r l y green. quinone sulfo-acid, let-black. e a s i l y (ExampleS, coloringsoluble matterA.) greenblue.

2. Paratoluidin brom- As paste Easily solu- Unchanged Fairly soluble green Soluble on Violet B rig h t sulfanihdo-a n th 1' a b la 0 k ble green. blue. boi l i n g, green. quinone sulfo acid green. b l n i s h (Example 5, coloringgreen matter A) sulfonated according to Example 7.

3. Coloring-matter B of As pow- Easilysolu- Unchanged Hot, soluble violet- H a r d ly Violet Greenish Example 5. der blueble blackblue. s 0 1n ble gray to 4 black. ish blue. green. black.

4. Anilin-l-brom-sulfanll- As paste Easilysolu Unchanged Hot, fairly Fairly sol- Insoluble Blu e vio- B ri g h t ldo-anthraq u 1 n o n e b l a ck ble bluish so 1 u b l e uble blue. let. green. snlfo-acid, (Example green. green. blue.

5.) Less soluble coloring-matter on further sulfonation.

5, Coloring-matter G of As paste Easily solu- Becomes greener But slight- B oi l i n g H a r d 1 y Dull blue Green.

Example 6. b l a c kble in hot ly soluble e a s i l y soluble.

green. w a t e r on boiling s o l uh I e b l u e blue. blue. green.

6. Col orrngmatter D of As paste Easilysolu- Becomes greener. Hot, solu- Fairly 501- But sllght- Bla c ki s 11 Gr ay to Example 6. b 1 a ck ble blackble blue. uble blue. 1y soluble violet. black green. green. olive. green.

. A g I Ido not wish to be understood as limiting myselfto the para to the exclusion of the meta variety of the sulfanilate.

Now what I claim is- 1. The process of manufacturing new coloring-matterof the anthracene series by condensing with aromatic amins the halogenized condensation products of nitro-anthraquichrome green to grayish or blackish green shades.

l. The new coloring-matter of the anthracene series such as can be obtained by condensing paratoluidin with a halogenized sulfanilido anthraquinone, which dissolves in water with a green color and in alcohol and in glacial acetic acid with a blue color, which gives a violet color with concentrated. sulfuric acid and which on further sulfonation becomes more easily soluble in alcohol and in glacial acetic acid and which in its mono or poly sulfonated form dyes chrome-mordanted wool a green shade.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

OSCAR BALLY.

Witnesses:

ERNEST E. EHRHARDT, JACOB ADRIAN.

a in the Patent Office.

[SEAL It is hereby certified that in Letters Patent No. 723,125, granted March 17, 1903, upon theapplication of Oscar Bally, of Mannheim, Germany, for an improvement in Green Anthracene Dye and process of making same, an error appears. in the printedspecifioation requiring correction, as follows: In lines 26-7, page 3, the word Sulfanilido should read Sulfoam'lido; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case Signed and sealed this 6th day of October, A. D., 1903.

F. I. ALLEN,

Commissioner of Patents. 

